Addition compounds of norbornadienes and quadricyclenes with bis(trifluoromethyl) thioketene and their s-oxides and s-dioxides



United States Patent 3,406,184 ADDITION COMPOUNDS OF NORBORNADIENES AND QUADRICYCLENES WITH BIS(TRIFLUORO- METHYL)THIOKETENE AND S-OXIDES AND S-DIOXIDES Maynard S. Raasch, Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed May 4, 1966, Ser. No. 547,437 12 Claims. (Cl. 260-327) ABSTRACT OF THE DISCLOSURE 6 hexafluoroisopropylidene-7-thiatetracyclo[3.2.1.1 0 ]nonanes and 4-hexafiuoroisopropylidene-3-thiatricyclo[4.2.*1.0 non-7-enes formed by reacting bis'(tri'fiuoromethyl)thioketene with norbornadienes and quadricyclenes, respectively, and their S-oxides and S-dioxides are claimed. The S-oxides and S-dioxides are formed by oxidation of the sulfides. The compounds are useful as plasticizers for polythiocarbonyl fluoride.

This invention relates to fluorine-containing polycyclic sulfur compounds, their S-oxides, their S-dioxides and to the proceses for the preparation of these products.

The product embodiment of this invention is directed to 6 hexafluoroisopropylidene-7-thiatetracyclo[3.2.1.1 0 ]nonanes, their S-oXides and S-dioxides (I), and to 4 hexafluoroisopropylidene-3-thiatricyclo[4.211.0 ]non- 7-enes, their S-oxides and S-dioxides (II). These products are of the formulae o s L c(cr wherein X is selected from the group consisting of hydrogen; a monovalent group R selected from alkyl, cycloalkyl, alkylcycloalkyl, aralkyl, aryl, alkaryl, fluoroalkyl, or fluoroaryl, chloroaryl; halogen; tertiary alkoxy; aryloxy; hydroxy; acyloxy; and RSO NH-; and n is an integer from 0 to 2. The monovalent group R contains up to 18 carbon atoms; aryl and aralkyl substituents contain carbocyclic aromatic rings selected from the group consisting of phenyl, biphenyl, naphthyl and the alkyl moiety of the aralkyl and alkaryl radicals contain up to 12 carbons.

The sulfide products of this invention, wherein n=0, are produced by the addition of bis(tn'fluoromethyl)- t-hioketene to 2,5-norbornadienes (III) and to tetracyclo- 3,406,184 Patented Oct. 15, 1968 ice '[2.2.l.0 .0 ]heptanes (quadricyclenes) (IV).

polycyclic reactants are of the formulae These III IV Stereoisomerism can occur in this situation since the carbon in the 9-position of the products is an asymmetrical center. The thiatricyclo[4.2.1.0 ]non-7-enes can also exist as endoand exo-isomers.

Bis(trifluoromethy1)thioketene used as a reactant in this invention is a new compound which has been described and claimed in my copending application, Ser. No. 249,606, filed J an. 7, 1963, now U.S. Patent No. 3,275,609. The preparation of this compound is described in Example A.

The sulfides of this invention are produced by contacting the cyclic reactant with bis(trifluoromethyl)thioketene at a temperature of 25-150 C. Temperatures of the order of C. are preferred. Bis(trifluorornethyl)ketene boils at 52 C., therefore reactions conducted above that temperature are preferably carried out in a closed vessel under autogenous pressures. This process can be conducted by either batch or continuous processes.

The proportions and mode of addition in which the reactants can be brought together to carry out the process of this invention are not critical and can be varied widely. High yields of the sulfides of this invention, based on the polycyclic reactant, are obtained when the molar ratio of the bis(trifiuoromethyl)thioketene to the polycyclic compound is about 1:1 to 6:1, and this range of ratios represents the preferred proportions. However, ratios in the range from 10:1 to 1:5 are operable to produce some of the desired product.

The reaction can be carried out in the presence of or absence of a liquid solvent medium which is inert to the reactants and products. Such inert solvents include hydrocarbons or halogenated hydrocarbons such as hexane, cyclohexane, benzene, toluene, carbon tetrachloride, dichlorotetrafluoroethane, chlorobenzene and the like. The sulfide products can be isolated and purified by conventional processes of distillation and/ or crystallization.

The process embodiment of this invention for producing S-oxides and S-dioxides of I and II, that is wherein n is 1 or 2, comprises contacting 6-hexafluoroisopropylidene-7-thiatetracyclo[3.2.1.1 .0 ]nonanes or 4-hexafluoroisopropylidene 3 thiatricyclo[4.2.1.0 ]non 7- enes with an oxidizing agent. Oxidizing agents which can be used include hydrogen peroxide, peracetic acid, perbenzoic acid, chromium trioxide, potassium permanganate and the like. S-oxides, which are also known as sulfoxides, are produced when the ratio of the equivalent of oxidizing agent to moles of the sulfide is about 2. S-dioxides, which are also known as sulfones, are produced when the ratio of equivalents of oxidizing agent to moles of the sulfide is about 4 or greater. S-dioxide can also be produced by oxidizing S-oxides with at least 2 equivalents of oxidizing agent per mole of S-oxide. An equivalent weight of oxidizing agent is the gram-molecular weight divided by the total change in valence of all atoms in the molecule which changes valence.

The oxidation process is generally conducted at a temperature of 100 C. In some cases lower and higher temperatures can be used. Solvents such as acetone and acetic acid can be used. Aqueous solutions of the oxidizing agent can be used. Oxidizing agent such as peracetic acid, prepared from 30% hydrogen peroxide and glacial acetic acid, is a preferred oxidant.

The S-oxides and S-diOXides are thermally stable products which are less volatile than the corresponding sulfides. S-oxides and S-dioxides can be isolated by distillation under reduced pressure and/or crystallization.

The preparation of numerous 2,5-norbornadienes has been reported in the chemical literature. 7-tertiary butoxy- 2,5-norbornadiene has been prepared by the reaction of norbornadiene with tertiary butyl perbenzoate. P. R. Story, I. Am. Chem. Soc., 82, 2085 (1960). 7-alkyl and 7-aryl- 2,5-norbornadienes can be prepared by the reaction of the corresponding alkyl and aryl magnesium halide with 7-t-butoxy-2,5-norbornadiene, P. R. Story and S. R. Fahrenholtz, J. Org. Chem., 28, 1817 (1963). 7-hydroxy- 2,5-norbornadiene has been prepared by S. Winstein, et al. reported in J. Am. Chem. Soc., 77, 4183 (1955). Acylation of this product with acylating agents such as organic acid anhydrides or halides yields the corresponding 7-ester derivatives.

The preparation of 7 methanesulfonamido 2,5 norbornadiene is described in Example 10. 7-alkylsulfonamidoand 7-arylsulfonamido derivatives can be produced by substitution of the appropriate alkyl or arylsulfonamide for methanesulfonamide in the procedure of Example 10.

The quadricyclene reactants can be prepared from the 7-substituted 2,5-norbornadiene by ultraviolet light photoisomerization according to the method of Hammond et al., J. Am. Chem. Soc., 83, 4674 (1961).

The process for the preparation of the products of this invention containing a hydroxyl group in the 9-position comprises saponification of esters prepared in the manner described above with 25% aqueous sodium hydroxide at a temperature of 50-100 C. The quantity of sodium hydroxide solution to ester should be at least a volume ratio of 1:1. Higher volume ratios are preferred. The 7-hydroxy substituted product is isolated from the reaction mixture by neutralization of the sodium hydroxide with a mineral acid such as hydrochloric or sulfuric acid, followed by solvent extraction using ether, chloroform and the like, and removal of the solvent.

The process of this invention for producing either the S-oxides or S-dioxides products of this invention comprises the step of (a) contacting bis(trifluoromethyl)thioketene with the cyclic reactant, (b) saponification of the product, (c) acidification of the reaction mixture with a mineral acid, (d) isolation of the product by solvent extraction followed by removal of the solvent by distillation, (2) oxidizing the product with a quantity of oxidant which' produces either the S-oxide or S-dioxide, and (1) recovery of the product produced.

The process steps b-e are omitted when the products desired are the sulfides wherein R is groups other than hydroxyl.

The process steps b-d are omitted when the products desired are S-oxides and S-dioxides wherein R is groups other than hydroxyl.

The process steps e and f are omitted when the products desired are the sulfides wherein R is hydroxyl.

The following examples further illustrate the invention.

Example A A 400-ml., stainless steel-lined tube containing 60 g. (0.149 mole) of 2,4-bis(dicarbethoxymethylene)-1,3-dithietane was cooled to C. and charged with 10 g. (0.5 mole) of hydrogen fluoride and g. (1.16 moles) of sulfur tetrafiuoride. The tube was heated with agitation for two hours each at 125 C. and C. and four hours at 200 C. It was then cooled to room temperature, bled of volatile products, cooled to 80 C; and charged again with 35 g. (1.75 moles) of hydrogen fluoride and 125 g. (1.16 moles) of sulfur tetrafluoride. The recharged tube was heated at 150 C. for two hours and 200 C. for four hours, cooled to room temperature and bled, and the contents were unloaded into a polyethylene bottle. The reaction product was poured onto ice and the crystalline solid which formed was separated by filtration and washed with water and 10% aqueous sodium carbonate solution. The product was then steam-distilled and filtered from the aqueous distillate. The moist crystals were dissolved in boiling methylene chloride, anhydrous magnesium sulfate was added to remove moisture, and the solution was filtered hot. Cooling of the filtrate gave 40 g. (69% yield) of 2,4-bis(hexafluoroisopropylidene)-1,3-dithietane in two crops. This product melts at 84.585.5 C. and boils at 173 C.

Analysis.Calcd. for C F S C, 24.75; F, 58.74; S, 16.52. Found: C, 24.96; F, 58.28; S, 16.83.

An apparatus for the pyrolysis of 2,4-bis(hexafiuoroisopropylidene)-1,3-dithietane was constructed of an unpacked platinum tube, 60 cm. long and 1.25 cm. in diameter, with stainless steel inner joints silver soldered to each end. The tube, fitted with thermocouples, was mounted in a cylindrical heater 30 cm. long, and the assembly was set on a vertical stand at a 30 angle. The lower end of the tube was connected to a glass trap protected with a drying tube and cooled in a Dry Ice-acetone mixture. The upper end of the tube was connected to a side arm of a distilling flask provided with a nitrogen inlet in its neck. The neck and side arm of the flask and the upper end of the pyrolysis tube were wrapped with glass cloth heating tape to keep these parts above the melting point (85 C.) of the dithietane.

The pyrolysis tube was heated at 650 C. and a total of 75 g. of 2,4-bis(hexafluoroisopropylidene)-1,3-dithietane was distilled through under a very slow stream of nitrogen during a 3-hour period. The product collected in the cold trap was distilled to give 50 g. (67% yield) of bis(trifluoromethyl)thioketene boiling at 5153 C., mostly 52 C., obtained as a reddish orange liquid, 11; 1.3502, D 1.462.

Analysis.-Calcd. for C F S: C, 24.75; F, 58.74; S, 16.52. Found: C, 24.95; F, 58.65; S, 1 6.54.

The structure is supported by the F nuclear magnetic resonance'spectrum, showing a single peak.

Example 1.-6-hexafluoroisopropylidene-7-thiatetracyclo[3.2.1.1 .0 ]nonane Norbornadiene (3.68 g., 0.04 mole) and 7.76 g. (0.04 mole) of bis(trifiuoromethyl)thioketene were sealed in a glass tube and heated at 100 C. for 16 hours. The resulting red liquid was distilled at 106-110 C. at mm. The distillate crystallized in part, and the crystals were filtered 011 and recrystallized from methanol to give 3.73 g. (33% yield) of the thiatetracy clononane, MP. 53- 53.5 C.

Analysis.-Calcd. for C H F S: C, 46.15; H, 2.82; S, 11.20. Found: C, 46.43; H, 3.14; S, 10.99.

In agreement with the structure, the P NMR. spectrum consists of two quadruplets. The H NMR. spectrum has a multiplet at 1.25-1.75 ppm. (3 protons), singlet at 1.85 p.-p.m. (2 protons) broad peak at 2.39 ppm. (1 proton), multiplet .at 3.37 ppm. (1 proton), and quadruplet at 3.52 ppm. (1 proton). No unsaturated CH is present. The infrared spectrum has a band at 620 ,u indicative of the exocyclic double bond.

Example 2.-6-hexafluoroisopropylidene-7-thiatetracyclo[3.2.1.1 .0 ]-nonane 7,7-dioxide To 2.86 g. (0.01 mole) of the compound of Example 1 was added ml. of acetic acid and 3 ml. (0.029 mole) of 30% hydrogen peroxide and the solution was heated on a steam bath for 4 hours. Water (20 ml.) was slowly added, the mixture was cooled, and the crystals were filr tered ofl. Recrystallization from methanol containing a little water gave 2.93 g. (92% yield) of the sulfone, M.P. 124.5-125 C.

Analysis.-Calcd. for C H F O S: C, 41.52; H, 2.53; S, 10.08. Found: C, 41.54; H, 2.74; S, 10.01.

Example 3.-6-hexafluoroisopropylidene-7-thiatetracyclo[3.2.1.1 .0 ]nonane 7-oxide Oxidation of the compound of Example 1 as in Example 2, but with use of a molar equivalent of hydrogen peroxide instead of an excess, gives the very soluble sulfoxide. The residue left by evaporation of the solvent may be crystallized from methanol by cooling in Dry Ice, but the product melts over a range around 40 C. because of the presence of two stereoisomers. Further oxidation of the sulfoxide with hydrogen peroxide yields the sulfone of Example 2.

Example 4.--9-chloro-6-hexafiu0roisopropylidene-7- thiatetracyclo[3.2.1.1 .0 ]nonane Example 5.9-tert-butoxy-6-hexafiuoroisopropylidene-7 thiatetracyclo[3.2.1. 1 .0 nonane 7-tert-butoxy-2,5-norbornadiene (13.02 g., 0.80 mole, commercially available) and 15.52 g. (0.08 mole) of bis(trifluoromethyl)thioketene were heated in a sealed glass tube at C. for 15 hours. The mixture was cooled, a little dichloromethane was added, and 6.9 g. of by-product thioketene dimer was filtered off. The filtrate was distilled at 70 C. and 0.05 mm. and part of the distillate crystallized. The crystals were filtered off, rinsed with methanol, cooled with Dry Ice, and recrystallized from methanol to give 4.48 g. (15.7% yield) of product melting at 72-73 C.

Analysis.-Calcd. for G i-1 F 03: C, 50.26; H, 4.50; S, 8.95. Found: C, 50.66; H, 4.60; S, 8.82.

The NMR. spectra show the structure to be analogous to that for the compound of Example 1.

The above crystalline compound is one of the two stereoisomers of the product, the second isomer being found in the liquid filtrate from the crystals. (The stereoisomerism depends on the orientation of the tert butoxy group with respect to the ring structure in the above formula. The specific orientation in the isomers is not known.)

Example 6.9-phenyl-6-hexafluoroisopropylidene-7- thiatetracyclo[3.2. l .1 0 nonane A mixture of 5.5 g. of 7-phenyl-2,5-norbornadiene (Story & Fahrenholtz, J. Org. Chem. 28, 1716 (1963)) and 6.4 g. (0.033 mole) of bis(trifiuoromethyl)thioketene was heated in a sealed glass tube at 100 C. for 16 hours. Dimer of the thioketene was filtered from the cooled product and the filtrate was distilled to give 3.8 g. (35% yield) of the thiatetracyclononane, B.P. 103-104 C. at

7 0.05 mm. This mixture of the two stereoisomers crystallized and melted at about 48-67 C.

Analysis.Calcd. for C H F S: C, 56.35; H, 3.34; S, 8.85. Found: C, 56.65; H, 3.58; S, 8.77.

Example 7.--9-trifluoroacetoxy-fi-hexafluoroisopropylidene-7-thiatetracyclo 3 .2. 1.1 .0 non ane OCOOF:

Example 8.--9-acetoxy-6-hexafiuoroisopropylidene-7- thiatetracyclo[3.2.1.1 .0 ]nonane COCH 2,5-norbornadiene-7-yl acetate and bis(trifiuoromethyl) thioketene were heated in a glass tube according to the procedure of Example 6 and the product was obtained by distillation at 61-65 C. at 0.15 mm.

Example 9.9-hydroxy-6-hexafluoroisopropylidene-7- thiatetracyclo 3 .2. 1. 1 .0 nonane A'l A To 2.76 g. (0.00684 mole) of the trifiuoroacetate of Example 7 in ml. of methanol was added 0.46 g. (0.00697 mole) of 85% potassium hydroxide in 3 ml. of methanol. The methanol was then evaporated off, water was added, and the product was collected by dissolving it in dichloromethane. After the product was dried over magnesium sulfate, it was distilled: B.P. 81 C. at 0.025 mm.; yield, 1.45 g. or 69%. The viscous liquid distillate crystallized, and was found to consist of a mixture of the two possible stereoisomers melting around 7293 C. Gas chromatography showed two close peaks.

Analysis.-Calcd. for C H F OS: C, 43.71; H, 2.67; S, 10.61. Found: C, 44.01; H, 2.72; S, 10.45.

The NMR. spectrum corresponded to the structure.

Example 10.9-(methanesulfonamido)-6-hexafiuoroisopropylidene-7-thiatetracyclo [3 ,2,1,1 '.0 ]nonane 7-(methanesulfonamido)-2,5-norbornadiene (1.85 g., 0.01 mole) and 11.64 g. (0.06 mole) of.-bis(trifluo'romethyl)thioketene were sealed in a glass tube and heated at C. for 15 hours. The excess thioketene dimerized and the dimer was removed from the product by heating at 100 C. at 15 mm. The residue was dissolved in carbon tetrachloride-and 0.6 g. of unreacted norbornadienecrystallized out of-thes'olutionon seeding. This was-filtered off. The filtrate was allowed to stand and the thiatetracyclononane crystallized out; yield, 0.19 g. or 5%. After recrystallization from methanol it melted at 177 C.

Analysis.-Calcd. for C H F NO S C, 37.99; H, 2.92; S, 16.90. Found: C, 38.37; H, 2.97; S, 16.92.

The NMR. spectrum is similar to that for the other examples, aside from the NH and CH peaks.

The 7-(methanesulfonamido)-2,5-norbornadiene for the above synthesis was made as follows: A mixture of 16.4 g. (0.1 mole) of commercially available 7-tertbutoxy-2,5-norbornadiene and 9.5 g. of methanesulfonamide were heated on a steam bath. Three drops of methanesulfonic acid were added, and stirring and heating were continued for 20 minutes. The mixture became homogeneous and crystallized on cooling. Recrystallization from carbon tetrachloride, gave 7 g. (38% yield) of 7-(methanesulfonamido)-2,5-norhornadiene, M.P. 110.5 C.

Analysis.Calcd. for C I-I NO S: C, 51.85; H, 5.98; S, 1730. Found: C, 51.99; H, 6.00; S, 17.63.

The NMR. spectrum in deuterochloroform shows a singlet at 2.96 p.p.rn. (CH split peak at 3.65 p.p.rn. (bridgehead protons), singlet at 3.79 p.p.rn. (bridge proton), broad singlet at 5.40 p.p.m. (NH), and quartet at 6.72 p.p.rn. (2 CH=CH)-.

Example 11.4-hexafiuoroisopropylidene-3-thiatricyc1o [4.2.1.0 non-7-ene To 4.60 g. (0.05 mole) of tetracyclo-[2210 .0 heptane [Quadricyclene. Hammond,-Turro, land Fischer, J. Am.'Chem. Soc. 83, 4674 (1961)] in 5 ml. of dichloromethane was slowly added 9.70 g. (0.05 mole) of bis (trifiuoromethyl)thioketene with stirring and cooling in ice. Distillation gave 10.4 g. (73% yield) of the thiatricyclononene, B.P. 39 C. at 0.08 mm., n 1.4655.

Analysis.Calcd. for C H F S: C, 46.15; H, 2.82; S, 11.20. Found: C, 46.51; H, 2.90; S, 11.42.

In accordance with the above structure, the proton NMR. spectrum shows a quartet centered at 1.76 p.p.rn. (bridge CH singlet at 2.83 p.p.m. (2 protons), singlet at 2.93 p.p.m; (1 proton), broad singlet at 3.33 p.p.rn. (1 proton), and singlet at 5.95 p.p.rn. (CH=CH).The P NMR. spectrum has two quadruplets. The infrared spectrum has bands at 3.25 ,n (='CH), 6.13 ,u. (exocyclic @C), and 6.38 ,m (cyclic C=C).

Example 12.4-hexafiuoroisopropylidene-3-thiatricyclo- '[4.2.1.0 ]n0n-7-ene 3,3-dioxide The product of Example 11 was oxidized with hydrogen peroxide in acetic acid at room temperature to give the S-dioxide.

Additional representative 6-hexafiuoroisopropylidenethyl, 4-n-hexy1phenyl, 4-dodecylphenyl, 4-n-hexylnaph- 7-thiatetracyclo[3.2.1.1 .0 ]nonanes corresponding to thyl, 3,4-dimethylphenyl, 3,4-dimethylnaphthyl, 3,4,5-tri- Formula I can be prepared by procedures illustrated in methylphenyl, cyclohexylmethyl, cyclopentylmethylcy- Examples 1-10. Likewise, representative 4-hexafluoroisoclohexyl, ethylcyclohexyl, hydroxy, chlorine, ethanesulpropylidene 3 thiatricyclo [4.2.1.0 ]non 7 enes cor- 5 fonarnido, lpropanesul-fonamido, butanesulfonamido, responding to Formula II can be prepared by the procepentanesulfonamido, cyclohexanesultonamido, dodecanedure of Example 11 and the corollary procedures of sulfonamido, octadecanesulfona-mido, benzenesulfon- Examples 2, 3 and 9. amido, naphthalenesulfonamido, chlorobenzenesulfona- Additional compounds of Formula I wherein n is 0 mido, phenylmcthanesulfonarnido, fluorobenzenesulfonaobtainable by addition of bis(trifluoromethyl)thioketene mido, p-methylbenzenesulfonamido, and acyloxy derivato substituted norbornadienes are shown in Table I. The tives such as 9-[2,5-norbornadienyl] and 9-[quadricyrepresentative X substituents are given, the intermediate clenyl] esters of the following acids: formic, propionic, norbornadienes and the thiatetracyclononaue products n-butyric, valeric, a-ethylisovaleric, cyclopentanecarboxbeing identified by name. ylic, trifluoroacetic, pentafluoropropionic, myristic, pal- TABLE I X Norbornadlene Intermediate Formula I Product Methyl 7-methyl-2,5-norbornadiene 9-methyl-6-hexafiuoroisopropylidene-7-thiatetraoyclo- {3.2.1.1 .0 ]nonane. Octyl 7octyl-2,5-norbornadiene 9-0etyl-fi-hexafiuoroisopropylidene'Z-thiatetracyclo- [3r2.1.1 .0 ]nonene.

CyclohexyL- 7-cyclohexyl-2,5-uorbornadiene.. 9-cyclohexy1-6-hexafiuoroisopropylldene-7-thiatetraeyclol3.2.1.1 .0 ]n0nane.

BenzyL-.. 7-benzyl-2,5-norbornadiene 9-benzyl-fi-hexafluorolsopropylidene-T-thiatetracyclo- [3.2.1.l .0 ]nonane.

Bromine 7-br0mo-2,5-norbornadiene 9-bromo-6'hexafluor0isopropylidene-7-thiatetracyclo- [3.2.l.1 .0 ]n0nane tert-Amyloxy 7-(tert-amy1oxy)-2,5-norbornadiene 9-(tert-amyloxy)-6-hexafluoroisopropylidene-Hhiatetracyclo[3.2.l.1 .0 ]nonane.

3-ethy1-3-hexyloxy 7-(3-ethyl-3-hexy1oxy)-2,5-norbornadiene 9-(3-ethyl-3-hexyloxy)-6-hexafluoroisopropylidene-7-thiatetraeyclo[3.2.Ll 'm -qnonane.

p-Toluoyloxy 7-(p-toluoyloxy)-2,5-norbornadiene 9-tp'toluoyloxy)-6-hexafluoroisopropylidene7-thiatetracyclo[3.2.1.l .0 ]nonane.

Cyelohexanecarbonyloxy. i1.... 7-(cyclohexaneearbonyloxy)-2,5-norbornadiene. 9-(cyclohexaneearbonyloxy)-6-hexafluoroisopropylidene-7- thiatetracyclo[3.2.l.l 'w qnonane.

Heptanoyloxy 7-heptanoyloxy-2,5-norbornadiene 9-heptanoyloxy-S-hexafluoroisopropylidene-7-thiatetracyclo[3.2.1.1 .0 ]nonane.

B-Naphthalenesulfonamido 7-(B-naphthalenesulfonarnido)-2,5-norbornadiene. 9-(B-Naphthalenesultonamido)-6-hexatluoroisopropylidene-7- thiatetraeyclo[3.2.1.l mlnonane. 4-methylcyclohexanesulfonemido.. 7-(4-methyleyclohexanesu1lonamido)-2,5- 9-(4-methylcyclohexanesulfonamido)-6-hexafluoroisopropylnorbornadiene. idene-7-thiatetraeyclo[3.2.1.l m -qnonane. Phenoxy 7-phenoxy-2,5-norbornadiene 9 henoxy-flhexafluoroisopropylidene-7-thiatetracyclo- 3.2.1.1 ,0 ]nonane.

Compounds of Formula II (n=0) obtainable by adrnitic, stearic, phenylacetic, p-isopropylphenylacetic, p-tdition of =bis(trifluoromethyl)thioketene to substituted 40 'butylbenzoic, diphenyl acetic, a-naphthoic acid and the tetracyclo[2.2.1.0 .0 ]heptenes are shown in Table II. like.

The table shows representative X-substituents together The compounds of this invention are useful as plaswith the corresponding intermediate quadricyclenes and ticizers for polythiocalrbonyl fluoride (CF S) This polythe thiatricyclo[4.2.1.0 ]non-7-ene products. mer is deficient in flow properties. It crystallizes at room TABLE II X Quadricyclene Intermediate Formula II Product Ethyl 7'ethyltetracyc1o [2.2.1.0 -.03,5]heptane 9-ethyH-hexafiuoroisopropylideue-3-thiatrieyc1o[4.2.1.0 ]non-7- Isoamyl 7-isoamyltetracyclo[2.2.Lo -w lheptane 9i ti tfmyI-4-hexafluoroisopropy1idene-3-thiatricyelolt.2.1.0 ]non- 2,4-dimethylphenyl. 7-(2,4-dimethylphenyl)tetracyclo[2.2.1.0 '.0 ]heptane... 9- +11exafluoroisopropylidene-3-thiatricyclo- 2-phenylethyl 7-(2 phenylethyl)tetracyelo[2.2.1.0 -".0 'flheptane 9-(fighfglfgggi-lgexafluoroisopropylidene-3-thiatricyclo- Fluorine 7-fiurotetracyelo[2.2.1.0 o lheptane 9-fluoro-4-hexafluoroisopropylidene-B-thiatricyclo[4.2.1.0 ]non-7- tert-Butoxy 7-(tert-bntoxy)tetracyclo[2.2.1.0 -.0= lheptane .1 i(323313337)4-11exafluoroisopropylidene-S-thiatrieyclo[4.2.1.0 Benzoyloxy 7-benzoyloxytetracyelo[2.2.1.0 -.0 ]heptane QJZIegZWgiIIog-Qhexafluoroisopropylidene-Il-thiatricyclo[4.2.1.0 Isobutyryloxy 7-isobutyryloxytetracyclo[2.2.LO .0 ]heptane 9dsgbfitlirgoxwi-hexafluoroisopropylideueJi-thiatrieyclo[4.2.1.0

Methanesulfonamido.-. 7-methanesulfonamidotetracyclol2.21.0.0 ]heptane -riiieghlelill e slulion lamido-4-hexafluoroisopropylidene-3-thiatricyclonon- -ene.

Included among the 7-substituted 2,5-norbornadienes temperature and during crystallization changes from an and 7-substituted quadricyclenes, which can be reacted elastomeric to a rigid form. The present compounds inwith bis(trifluoromethyl)thioketene to produce the 9- crease the flowability of the polymer in molding operasubstituted sulfides of this invention are, 2,5-norbornations and inhibit the loss of desirable elastic properties. dienes and quadricyclenes substituted in the 7-position The plasticizer may be incorporated in the polymer by with the following groups: n-propyl, isopropyl, n-butyl, soaking 4 parts of polymer in a solution of 1 part of a isobutyl, sec-butyl, pentyl, n-hexyl, 2-ethylhexyl, n-decyl, compound of this invention dissolved in 1.5 parts of n-dodecyl, n-tetradecyl, n-octadecyl, cyclopentyl, cyclochloroform. The swollen polymer is then dried at C. octyl, cyclododecyl, a-phenylethyl, a-phenyloctyl, l-naphand may be molded at C. thylmethyl, 2-napl1thy1ethyl, 2,2,3,3-tetrafiuoron-propyl, The plasticizing elfects of the compounds are not lim- 2,2,3,3,4,4,5,5-octafiuoro-n-pentyl, p-fiuorophenyl, pentaited to the above specialty polymer. Vinyl polymers and fluorophenyl, chlorophenyl, Z-methyI-n-butoxy, triethylrubbers may also he plasticized using the compounds of methoxy 4-methoxyphenyl, 4-e-thylphenyl, 4-methylnaph- 75 this invention.

wherein X is a member selected from the group containing up to 18 carbon atoms consisting of hydrogen; hydroxy; a monovalent group R selected from alkyl, cycloalkyl, alkylcycloalkyl, aryl, alkaryl, fiuoroalkyl, fluoroaryl, chloroaryl, or aralkyl; halogen; tertiary alkoxy; aryloxy; RCOO- and RSO NH; and n is an integer from to 2.

2. The compound of claim 1 wherein X is phenyl and n is 0, said compound being 9-phenyl-6-hexafiuoroisopropylidene-7-thiatetracyclo[3.2.1.1 .0 ]nonane.

3. Compound of claim 1 wherein X is hydrogen and n is 1, said compound being 6-hexafiuoroisopropylidene-7- thi-atetracyclo[3.2.1.1 20 ]nonane 7-oxide.

4. A compound of claim 1 wherein X is hydrogen and n is 0, said compound being 6-hexafiuoroisopropylidene- 7-thiatetracyclo[3.2.1.1 .0 ]nonane.

5. A compound of claim 1 wherein X is hydrogen and n is 0, said compound being 4-hexafluoroisopropylidene- 3-thiatricyclo[4.2.1.0 ]non-7-ene.

6. A compound of claim 1 wherein X is hydrogen and n is 2, said compound being 6-hexafluoroisopropylidene- 7-thiatetracyclo[3.2.1.l .0 ]nonane 7,7-dioxide.

7. A compound of claim 1 wherein X is hydrogen and n is 2, said compound being 4-hexafluoroisopropylidene- 3-thiatricyclo[4.2.1.0 ]non-7-ene 3,3-dioxide.

8. Process for preparing a compound of claim 1 comprising the steps (a) contacting bis(trifiuoromethyl)thioketene with a compound selected from the group consisting of and 12 wherein X is as defined in claim 1 wherein said step is conducted at a temperature of 25150 C.,

(b) contacting the product obtained in step (a) with 5-25% aqueous sodium hydroxide, at a temperature of 50-100 C. wherein the volume ratio of the product of step (a) and aqueous sodium hydroxide is at least 111,

(c) reacting the reaction mixture of step (b) with the quantity of dilute mineral acid required to neutralize the aqueous sodium hydroxide,

(d) recovering a product produced thereby.

9. Process for producing a compound of claim 1 comprising the steps (a) contacting bis(trifiuoromethyl)thioketene with a compound selected from the group consisting of and wherein X is as defined in claim 1 wherein said step is conducted at a temperature of 25-150 C.,

(b) contacting the product obtained in step (a) with 5-25% aqueous sodium hydroxide, at a temperature of 50-100 C. wherein the volume ratio of the product of step (a) and aqueous sodium hydroxide is at least 1:1,

(0) reacting the reaction mixture of step (b) with the quantity of dilute mineral acid required to neutralize the aqueous sodium hydroxide,

(d) contacting the product of step (c) with an oxidizing agent at a temperature of 0100 C.,

(e) isolating the product produced by solvent extraction followed by removal of solvent,

(f) recovering the product produced thereby.

10. Process of claim 8 wherein step (a) is conducted in a liquid solvent medium inert to the reactant and product.

11. Process of claim 8 wherein the reactant is 2,5-norbornadiene.

12. Process of claim 8 wherein the reactant is quadricyclene.

References Cited UNITED STATES PATENTS 12/1952 Wilkes 260-332.1 5/1966 Hostettler et al. 260-327 OTHER REFERENCES JAMES A. PATTEN, Primary Examiner. 

